CN112979930A - Preparation of high biomass polyester polyols from hydrogenated itaconic acid - Google Patents
Preparation of high biomass polyester polyols from hydrogenated itaconic acid Download PDFInfo
- Publication number
- CN112979930A CN112979930A CN201911292836.2A CN201911292836A CN112979930A CN 112979930 A CN112979930 A CN 112979930A CN 201911292836 A CN201911292836 A CN 201911292836A CN 112979930 A CN112979930 A CN 112979930A
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- China
- Prior art keywords
- acid
- polyester polyol
- polyol
- reaction
- glycol
- Prior art date
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- Granted
Links
- 229920005906 polyester polyol Polymers 0.000 title claims abstract description 60
- 239000002028 Biomass Substances 0.000 title claims abstract description 37
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 title abstract description 5
- 238000002360 preparation method Methods 0.000 title description 4
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 claims abstract description 76
- 241001550224 Apha Species 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000002253 acid Substances 0.000 claims description 42
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 239000003963 antioxidant agent Substances 0.000 claims description 23
- 230000003078 antioxidant effect Effects 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 19
- -1 alkyl polyol Chemical class 0.000 claims description 15
- 229920005862 polyol Polymers 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 150000003077 polyols Chemical class 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 239000000539 dimer Substances 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 claims description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- CZZVAVMGKRNEAT-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)CO.OCC(C)(C)C(O)=O CZZVAVMGKRNEAT-UHFFFAOYSA-N 0.000 claims description 2
- PTPIRFSXRFIROJ-UHFFFAOYSA-N 2-(3-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=CC(O)=C1 PTPIRFSXRFIROJ-UHFFFAOYSA-N 0.000 claims description 2
- CTNICFBTUIFPOE-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=C(O)C=C1 CTNICFBTUIFPOE-UHFFFAOYSA-N 0.000 claims description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- VYZKQGGPNIFCLD-UHFFFAOYSA-N 3,3-dimethylhexane-2,2-diol Chemical compound CCCC(C)(C)C(C)(O)O VYZKQGGPNIFCLD-UHFFFAOYSA-N 0.000 claims description 2
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 claims description 2
- BUUSNVSJZVGMFY-UHFFFAOYSA-N 4-ethylheptane-3,3-diol Chemical compound CCCC(CC)C(O)(O)CC BUUSNVSJZVGMFY-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N alpha-octadecene Natural products CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 229940038384 octadecane Drugs 0.000 claims description 2
- AZJXQVRPBZSNFN-UHFFFAOYSA-N octane-3,3-diol Chemical compound CCCCCC(O)(O)CC AZJXQVRPBZSNFN-UHFFFAOYSA-N 0.000 claims description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012974 tin catalyst Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims 2
- CVNPKVXQUCOSOI-UHFFFAOYSA-N 3-ethylheptane-2,3-diol Chemical compound CCCCC(O)(CC)C(C)O CVNPKVXQUCOSOI-UHFFFAOYSA-N 0.000 claims 1
- 229940113120 dipropylene glycol Drugs 0.000 claims 1
- MGPUUXGHLCLLKJ-UHFFFAOYSA-N dodecanedioic acid;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.OC(=O)CCCCCCCCCCC(O)=O MGPUUXGHLCLLKJ-UHFFFAOYSA-N 0.000 claims 1
- 229940051250 hexylene glycol Drugs 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229920002635 polyurethane Polymers 0.000 description 12
- 239000004814 polyurethane Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 9
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 5
- 150000007519 polyprotic acids Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-NJFSPNSNSA-N Carbon-14 Chemical compound [14C] OKTJSMMVPCPJKN-NJFSPNSNSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000035 biogenic effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to the production of high biomass polyester polyols from hydrogenated itaconic acid, and in particular to high biomass polyester polyols, especially polyester polyols comprising hydrogenated itaconic acid, i.e., 2-methylsuccinic acid (2-mSA). Compared with the existing biomass polyester polyol, the polyester polyol with high biomass content provided by the invention meets APHA chromaticity specification, and is beneficial to further application. The invention also relates to a method for producing high biomass polyester polyols.
Description
Technical Field
The present invention relates to high biomass content polyester polyols, particularly containing hydrogenated itaconic acid (i.e., 2-methylsuccinic acid (2-mSA)). Compared with the existing biomass polyester polyol, the polyester polyol with high biomass content provided by the invention meets APHA (American public health Association) color specification, and can obtain polyurethane with good transparency, softness and high reverse elasticity when being further applied to the preparation of polyurethane. Also relates to a method for producing the polyester polyols with a high biomass content.
Background
Petroleum is the most important energy source in the world, and petrochemicals are ubiquitous, including small molecule compounds and polymers, such as polyurethanes, etc. The polyols required for preparing polyurethanes are generally prepared by the glycidyl synthesis of dicarboxylic acids and diols. However, as the use of petroleum increases worldwide, the reserves of petroleum are decreasing year by year, and from the perspective of continuous development, the substitution of biomass for petrochemicals is a necessary direction for the development of future industries, and some products in europe and america have already begun to be commercialized.
Although biomass dibasic alcohol can be prepared in the prior art, most biomass dibasic carboxylic acid is straight chain dibasic acid, and most of the prepared polyester polyol has crystallinity, so the development and the application of biomass polyurethane are greatly limited.
The common biogenic dibasic acids in the market comprise succinic acid, 2-methylsuccinic acid (2-mSA) and the like,
and it is known that 2-mSA can be prepared by fermentation using bioglycerol or corn starch and attempts have been made to solve the problems caused by straight chain dibasic acids using 2-mSA as a reactive monomer. However, in the prior art, no matter 2-mSA produced from petrochemical or biomass sources, which has a high content of iron ions, if 2-mSA with a content of more than 30 mol% is used in the polyester polyol formulation, it is difficult to obtain polyester polyol with satisfactory chromaticity (the chromaticity specification of polyester polyol in the industry falls to 40-100 APHA chromaticity or lower).
There is therefore still a need for polyester polyols, in particular for biopolyester polyols, which meet the requirements with regard to color.
Disclosure of Invention
The invention relates to polyester polyols which meet the requirements of color and are high in biomass content, in particular high in contents of 2 to mSA and have a color of <30 APHA.
The invention also relates to a method for preparing said polyester polyols, comprising the step of using a two-component antioxidant in the process.
Detailed Description
The invention is described in more detail in the following paragraphs. Each aspect so described may be combined with any other aspect unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
In the context of the present invention, unless the context dictates otherwise, the terms used are to be construed in accordance with the following definitions.
As used herein, the singular forms "a" and "the" include singular and plural referents unless the context clearly dictates otherwise.
As used herein, the term "comprising" is synonymous with "including" or "containing" and is inclusive or open-ended and does not exclude other unrecited members, elements or method steps.
The recitation of numerical endpoints includes all numbers and fractions subsumed within the respective range, as well as the recited endpoint.
Unless defined otherwise, all terms (including technical and scientific terms) used to disclose the invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. By way of further guidance, the term definitions are included to better understand the teachings of the present invention.
The invention relates to polyester polyols which meet the requirements of color and are high in biomass content, in particular high in contents of 2 to mSA and have a color of <30 APHA.
High biomass polyester polyols
The polyester polyol is obtained by esterification of a polyol and a polybasic acid, and the characteristics of the reaction monomer and the polyester polyol will be described below.
Polyhydric alcohols
Polyol means a hydrocarbon derivative having two or more hydroxyl groups (-OH). In the present invention, for example, alkyl polyols, unsaturated or aromatic polyols may be used. Biomass based polyols may also be used. As a reactive monomer for the polyester polyol. The number of hydroxyl groups of the hydrocarbon derivative can also be expressed, for example, by diol, triol …, and the like.
In the present invention, it is preferable to use (cyclo) alkyl diol as a reactive monomer. Examples of the polyhydric alcohol include, but are not limited to, diols having 2 to 12 and 36 carbon atoms, such as one or more of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, 2-methyl-1, 3-propanediol, hexanediol, dipropylene glycol, butylethylpropanediol, diethylpentanediol, 3-methyl-1, 5-pentanediol, 1, 4-cyclohexyldimethanol, cyclohexanediol, dodecanediol, spiroglycol, trimethylpentanediol, pentanediol, hydroxypivalic acid neopentyl glycol monoester, ethylhexanediol, dodecanediol, and the like, hydroquinone dihydroxyethyl ether, resorcinol dihydroxyethyl ether, trimethylolpropane, glycerol, trimethylolethane, 1,2, 6-hexanetriol, and the like. In one embodiment of the invention, ethylene glycol and butylene glycol are used as reactive monomers; in one embodiment of the invention, propylene glycol is used as the reactive monomer.
Polybasic acid
The polybasic acid refers to a hydrocarbon derivative having two or more carboxyl groups (-COOH). In the present invention, for example, alkyl polybasic acids, unsaturated or aromatic polybasic acids may be used. As a reactive monomer for the polyester polyol. The number of carboxyl groups contained in the hydrocarbon derivative is also indicated, for example, by dibasic acid, tribasic acid …, and the like.
In the present invention, it is preferable to use an alkyl dibasic acid as a reactive monomer, including at least 2-methylsuccinic acid (2-mSA) as a reactive monomer, since the structure of 2-mSA has a pendant methyl group, exhibiting a steric effect, so that the soft segment of polyurethane exhibits preferable flexibility. In addition, the side chain methyl increases the distance between molecules, so that the steric hindrance is increased, and the regularity of a molecular chain is reduced. Therefore, the structure does not damage Tg, can reduce Tm and endows the polyester polyol with unique performance on polyurethane. It can also be used in combination with other biomonomers, such as, for example, biosuccinic acid.
Other dibasic acids having a carbon number of 4 to 36 may be further used as the reactive monomer, examples include, but are not limited to, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecandioic acid; terephthalic acid, isophthalic acid, phthalic anhydride; 1, 4-cyclohexanedicarboxylic acid, octadecane unsaturated fatty acid dimer, maleic anhydride, etc. In one embodiment of the invention, at least 30 mole% of 2-mSA, preferably at least 32 mole% of 2-mSA, and more preferably at least 40 mole% of 2-mSA, based on the total moles of reactant monomers used, is used. In one embodiment of the present invention, at least 60 mole%, at least 70 mole%, at least 80 mole%, or at least 90 mole% of 2-mSA, or only 2-mSA, based on the total moles of polyacid monomers used, is used as the reactive monomer for the polyacid. Anhydrides or esters of the foregoing acids may also be used as reactive monomers.
Characteristics of
The polyester polyol provided by the invention has high biomass content and meets the requirements of the current sustainable development. Biomass content > 30%, preferably > 40%, more preferably > 50%, for example within a reasonable range consisting of the following endpoints: 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%. In one embodiment of the present invention, the biomass content of the polyester polyol is 30% to 100%, preferably 50% to 100%, and more preferably 80% to 100%. The existing international detecting instrument for biomass material content comprises a ratio counter, a liquid scintillation counter and an accelerator mass spectrometer, wherein a test target substance is a carbon 14(14C) isotope in a sample, and the content of a biomass carbon source, namely the biomass content, is calculated after the test target substance is compared with a standard value.
In one embodiment of the present invention, the polyester polyol exhibits an APHA color of no greater than 30, preferably no greater than 20, and more preferably no greater than 15.
In one embodiment of the present invention, the weight average molecular weight of the high biomass content polyester polyol is in the range of 500-: 600. 700, 800, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000, 3200, 3400, 3600, 3800, 4000, 4200, 4400, 4600, or 4800, preferably 1,000 to 4,000. Because polyester polyol can be used as a soft segment part when polyurethane is synthesized, the polyester polyol with high biomass content provided by the invention has high proportion in polyurethane if the molecular weight of the polyester polyol is too high, the degradation speed of the polyurethane is possibly too fast, and the polyurethane cannot be easily applied to market products; too low a molecular weight of the polyester polyol results in a low soft segment fraction, which may result in a polyurethane that is too stiff and inelastic. Therefore, in one embodiment, the molecular weight of the polyester polyol with high biomass content is adjusted to be 1000-4000 by adjusting the synthesis formula, so that products (high elasticity, high toughness and high reverse-dialing elasticity) meeting the market requirements can be prepared more easily, and the physical property maintenance rate can reach more than three years.
In one embodiment of the invention, the high biomass polyester polyol has an acid number in the range of <2mgKOH/g, preferably <1mgKOH/g, more preferably <0.5 mgKOH/g. If the acid value is too high, hydrolysis is easy, for example, if the acid value is higher than 2mgKOH/g, hydrolysis resistance and reactivity are poor, and a hydrolysis resistant agent may be required to be added to improve hydrolysis resistance.
In one embodiment of the present invention, the hydroxyl value of the high biomass polyester polyol is in the range of 15 to 220mgKOH/g, preferably 20to 140mgKOH/g, and more preferably 28 to 100 mgKOH/g.
Preparation method of polyester polyol with high biomass content
As described above, the process for producing a polyester polyol of the present invention comprises reacting 2-methylsuccinic acid with a diol and optionally a further dibasic acid.
In one embodiment of the present invention, the method for preparing a polyester polyol with high biomass content comprises at least the following steps:
(1) adding an alkyl polyol, an alkyl polyacid and an antioxidant system to a reactor;
(2) reacting at a temperature not higher than 160 ℃ in a stable gas environment, and then increasing the reaction temperature to 180-230 ℃ for further reaction;
(3) when the acid value is lower than the first target value, applying vacuum condition to the reactor and continuing the reaction;
(4) the reaction is completed when the acid value is lower than a second target value;
wherein the alkyl polyacid comprises at least 2-methylsuccinic acid and the antioxidant system comprises at least two antioxidants.
In one embodiment of the present invention, the stable gas of step (2) comprises nitrogen, inert gas, etc. In one embodiment of the present invention, the reaction of step (2) further comprises the use of a catalyst, examples of which include, but are not limited to, one or more of tin catalysts (e.g., T-9 catalysts, T-12 catalysts), titanium catalysts (e.g., TBT), bismuth catalysts, zinc catalysts, and the like.
In one embodiment of the present invention, the antioxidant system comprises a phosphite, hindered amine complex antioxidant. Examples of phosphite antioxidants may be antioxidants 168, 618, 626. An example of a hindered amine complex antioxidant can be antioxidant 5057.
In one embodiment of the present invention, the reaction in step (2) is performed at a temperature not higher than 160 ℃, 130 to 150 ℃, preferably 135 to 145 ℃, more preferably 138 to 142 ℃ or about 140 ℃, or at a temperature in a reasonable range composed of the above numerical ranges for 0.5 to 5 hours, preferably 0.5 to 3 hours, more preferably 1 to 2 hours, if the reaction time is too short, the reaction of acid and alcohol is incomplete, the monomer residue is more, the monomer heat resistance is poor, the chromaticity of the finished product is poor, the reaction time is too long, the overall synthesis reaction time is prolonged, the catalyst is deteriorated with the reaction time, and the acid value is difficult to be reduced; then raising the reaction temperature to 180-230 ℃, preferably at the temperature of 200-230 ℃. Without being limited by theory, it is known that since 2-methylsuccinic acid contains pendant groups, the reaction rate may be slow, and the monomer has poor heat resistance, the reaction is first carried out at a lower temperature; if the reaction is carried out directly at a temperature higher than 180 ℃, the problem of color depth is easily caused. In addition, the 2-methylsuccinic acid obtained from biomass sources generally has a higher content of iron ions, so that the color of the polyester polyol prepared from the 2-methylsuccinic acid is higher than that of the polyester polyol prepared from petrochemical-derived dibasic acid.
In one embodiment of the present invention, the biomass polyester polyol containing 2-methylsuccinic acid can be used to prepare polyester polyol with weight average molecular weight of 500-6000.
In one embodiment of the present invention, the first target value of step (3) is less than 30mgKOH/g, preferably less than 25mgKOH/g, more preferably less than 20 mgKOH/g. In one embodiment of the present invention, the second target value of step (4) is less than 1mgKOH/g, preferably less than 0.8mgKOH/g, more preferably less than 0.5 mgKOH/g. In one embodiment of the present invention, the vacuum condition of step (3) may be <60torr (vacuum > -700torr)
Material
Antioxidant 168: CAS number 315710-04-4.
Antioxidant 5057: CAS number 68411-46-1.
Antioxidant 1010: CAS number 6683-19-8.
T-9 catalyst: CAS number 301-10-0, stannous isooctanoate.
T-12 catalyst: CAS No. 77-58-7, dibutyltin dilaurate.
TBT: CAS number 5593-70-4, tetra-n-butyl titanate.
Examples of the invention
Example 1
Mixing 2-methylsuccinic acid (2-mSA): 400g, Ethylene Glycol (EG): 100g, Butanediol (BG): 150g, antioxidant 168: 0.06g, antioxidant 5057: 0.02g, T-9 catalyst: 0.08g of the mixture is added into a reaction vessel, nitrogen is introduced into the reaction vessel, the mixture is heated to 140 ℃ and stirred for 1 hour, the mixture is heated to 180-230 ℃ for reaction, when the acid value is lower than 20mg KOH/g, the vacuum degree is pumped to gradually increase to-720 torr, the temperature is maintained for 7 hours, and the reaction is stopped when the acid value is lower than 1.
Example 2
Mixing 2-methylsuccinic acid: 400g, ethylene glycol: 98g, butanediol: 140g, antioxidant 168: 0.06g, antioxidant 5057: 0.02g, T-9 catalyst: 0.08g, adding into a reaction vessel, introducing nitrogen, heating to 140 deg.C, stirring for 1hr, heating to 180-230 deg.C, reacting, vacuumizing when acid value is less than 20mg KOH/g to gradually increase vacuum to-720 torr, maintaining temperature for 7 hr, stopping reaction when acid value is less than 1
Example 3
Mixing 2-methylsuccinic acid: 400g, Propylene Glycol (PG): 280g, antioxidant 168: 0.06g, antioxidant 5057: 0.02g, T-9 catalyst: 0.08g of the mixture is added into a reaction vessel, nitrogen is introduced into the reaction vessel, the mixture is heated to 140 ℃ and stirred for 1 hour, the mixture is heated to 180-230 ℃ for reaction, when the acid value is lower than 20mg KOH/g, the vacuum degree is pumped to gradually increase to-720 torr, the temperature is maintained for 7 hours, and the reaction is stopped when the acid value is lower than 1.
Example 4
Mixing 2-methylsuccinic acid: 400g, propylene glycol: 250g, antioxidant 168: 0.06g, antioxidant 5057: 0.02g, T-9 catalyst: 0.08g of the mixture is added into a reaction vessel, nitrogen is introduced into the reaction vessel, the mixture is heated to 140 ℃ and stirred for 1 hour, the mixture is heated to 180-230 ℃ for reaction, when the acid value is lower than 20mg KOH/g, the vacuum degree is pumped to gradually increase to-720 torr, the temperature is maintained for 7 hours, and the reaction is stopped when the acid value is lower than 1.
Example 5
2-methylsuccinic acid: 400g, propylene glycol: 242g, antioxidant 168: 0.06g, antioxidant 5057: 0.02g, T-9 catalyst: 0.08g of the mixture is added into a reaction vessel, nitrogen is introduced into the reaction vessel, the mixture is heated to 140 ℃ and stirred for 1 hour, the mixture is heated to 180-230 ℃ for reaction, when the acid value is lower than 20mg KOH/g, the vacuum degree is pumped to gradually increase to-720 torr, the temperature is maintained for 7 hours, and the reaction is stopped when the acid value is lower than 1.
Example 6
2-methylsuccinic acid: 400g, propylene glycol: 242g, antioxidant 168: 0.06g, antioxidant 5057: 0.02g, TBT catalyst: 0.08g of the mixture is added into a reaction vessel, nitrogen is introduced into the reaction vessel, the mixture is heated to 140 ℃ and stirred for 1 hour, the mixture is heated to 180-230 ℃ for reaction, when the acid value is lower than 20mg KOH/g, the vacuum degree is pumped to gradually increase to-720 torr, the temperature is maintained for 7 hours, and the reaction is stopped when the acid value is lower than 1.
Comparative example 1
Mixing 2-methylsuccinic acid: 400g, ethylene glycol: 100g, butanediol: 150g, antioxidant 1010: 0.1g, TBT: 0.08g of the mixture is added into a reaction container, nitrogen is introduced into the reaction container, the mixture is heated to 180-230 ℃ and stirred, when the acid value is lower than 20mg KOH/g, the vacuum degree is pumped to-720 torr gradually, the temperature is maintained for 7 hours, and the reaction is stopped when the acid value is lower than 1.
Comparative example 2
Mixing 2-methylsuccinic acid: 400g, propylene glycol: 250g, antioxidant 1010: 0.1g, TBT: 0.08g of the mixture is added into a reaction container, nitrogen is introduced into the reaction container, the mixture is heated to 180-230 ℃ and stirred, when the acid value is lower than 20mg KOH/g, the vacuum degree is pumped to-720 torr gradually, the temperature is maintained for 7 hours, and the reaction is stopped when the acid value is lower than 1.
Comparative example 3
Mixing 2-methylsuccinic acid: 400g, ethylene glycol: 100g, butanediol: 150g, antioxidant 168: 0.06g, antioxidant 5057: 0.02g, T-9 catalyst: 0.08g of the mixture is added into a reaction container, nitrogen is introduced into the reaction container, the mixture is heated to 180-230 ℃ and stirred, when the acid value is lower than 20mg KOH/g, the vacuum degree is pumped to-720 torr gradually, the temperature is maintained for 7 hours, and the reaction is stopped when the acid value is lower than 1.
Performance evaluation
The following methods were used to evaluate the properties of the example polyester polyols.
Acid value: testing according to ASTM D4662
Hydroxyl value: testing according to ASTM D6342
APHA color number: testing according to ASTM D4890
The polyester polyol provided by the invention achieves the aim of high biomass content and simultaneously shows excellent APHA chroma value.
Claims (14)
1. A polyester polyol made from a polyol and a polyacid, wherein the polyol comprises at least one alkyl polyol and the polyacid comprises at least 2-methylsuccinic acid, and wherein the polyester polyol has an APHA color of no greater than 30.
2. The polyester polyol of claim 1, wherein the proportion of 2-methylsuccinic acid is at least 30 mole percent, based on the total moles of reactant monomers used.
3. The polyester polyol of claim 1, wherein the polyol comprises ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, 2-methyl-1, 3-propanediol, hexylene glycol, dipropylene glycol, butylethylpropylene glycol, diethylpentanediol, 3-methyl-1, 5-pentanediol, 1, 4-cyclohexyldimethanol, cyclohexanediol, dodecanediol, spiroglycol, trimethylpentanediol, pentanediol, hydroxypivalic acid neopentyl glycol monoester, ethylhexanediol, dodecanediol, hydroquinone dihydroxyethyl ether, resorcinol dihydroxyethyl ether, trimethylolpropane, glycerol, trimethylolethane, 1,2, 6-hexanetriol, or a combination thereof.
4. The polyester polyol of claim 1, wherein the polyacid further comprises succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid; terephthalic acid, isophthalic acid, phthalic anhydride; 1, 4-cyclohexanedicarboxylic acid, dimer acid octadecane unsaturated fatty acid dimer, maleic anhydride, or combinations thereof.
5. The polyester polyol of claim 1, wherein the polyester polyol has an acid number < 2.
6. The polyester polyol of claim 1, wherein the weight average molecular weight of the polyester polyol is from 1000 to 4500.
7. A method for preparing a high biomass content polyester polyol comprising the steps of:
(1) adding a polyol, a polyacid and an antioxidant system to a reactor;
(2) reacting at a temperature not higher than 160 ℃ in a stable gas environment, and then increasing the reaction temperature to 180-230 ℃ for further reaction;
(3) when the acid value is lower than the first target value, applying vacuum condition to the reactor and continuing the reaction;
(4) the reaction is completed when the acid value is lower than a second target value;
wherein the polyol comprises at least one alkyl polyol, the polyacid comprises at least 2-methylsuccinic acid, and the antioxidant system comprises at least two antioxidants.
8. The method of claim 7, wherein step (1) further comprises adding one or more of tin catalyst, titanium catalyst, bismuth catalyst, zinc catalyst, etc.
9. The method of claim 7, wherein the first target value is <30 mgKOH/g.
10. The method of claim 7, wherein the second target value is <1 mgKOH/g.
11. The method of claim 7, wherein the polyester polyol has a proportion of 2-methylsuccinic acid of at least 30 mole percent, based on the total moles of reactant monomers used to prepare the polyester polyol.
12. The method of claim 7, wherein the polyester polyol has an APHA color of no greater than 30.
13. The method of claim 7, wherein the polyester polyol has a weight average molecular weight of 1000 to 4500.
14. The method of claim 7, wherein the oxidizing agent comprises a phosphite antioxidant and a hindered amine complex antioxidant.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08301968A (en) * | 1995-04-28 | 1996-11-19 | Kuraray Co Ltd | Production of polyurethane |
| CN105218792A (en) * | 2015-10-16 | 2016-01-06 | 广东大盈化工有限公司 | Environment-friendly type polyester polyvalent alcohol and preparation method thereof |
| CN105399937A (en) * | 2015-12-16 | 2016-03-16 | 南京工业大学 | Preparation method of polyester polyol |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08301968A (en) * | 1995-04-28 | 1996-11-19 | Kuraray Co Ltd | Production of polyurethane |
| CN105218792A (en) * | 2015-10-16 | 2016-01-06 | 广东大盈化工有限公司 | Environment-friendly type polyester polyvalent alcohol and preparation method thereof |
| CN105399937A (en) * | 2015-12-16 | 2016-03-16 | 南京工业大学 | Preparation method of polyester polyol |
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